Photographic silver halide light-sensitive element

ABSTRACT

A PHOTOGRAPHIC SILVER HALIDE LIGHT-SENSITIVE ELEMENT COMPRISING A SUPPORT BEARING AT LEAST ONE LAYER CONTAINING AT LEAST ONE OF ANTI-PLUMMING AGENTS, SAID BEING PRESENT IN SAID LAYER AS A FINE DISPERSION OF A SOLUTION THEREOF IN A NON-VOLATILE ORGANIC SOLVENT, SAID SOLVENT BEING SUBSTANTIALLY SPARINGLY SOLUBLE IN WATER UNDER THE CONDITION OF PREPARING PHOTOGRAPHIC LIGHT-SENSITIVE ELEMENTS BUT DISSOLVED OUT OF SAID LAYER UNDER THE CONDITION OF DEVELOPING SAID LIGHT-SENSITIVE ELEMENT.

United States Patent 3,585,036 PHOTOGRAPHIC SILVER HALIDE LIGHT- SENSITIVE ELEMENT Kazuya Sano and Kinji Ohkubo, Kanagawa, Japan, as-

;ignors to Fuji Photo Film Company, Ltd., Kanagawa,

a an N5 Drawing. Filed Feb. 1, 1968, Ser. No. 702,171 Claims priority, applicatgonlsJapan, Feb. 1, 1967,

Int. or. trim 1/06 U.S. CI. 96-76 6 Claims ABSTRACT OF THE DISCLOSURE BACKGROUND OF THE INVENTION The present invention relates to a photographic silver halide light-sensitive element having a layer containing an anti-plumming agent, and more particularly, it relates to a photographic silver halide light-sensitive element having a layer containing fine dispersions of a solution of an antiplumming agent in a hydrophobic solvent.

Silver halide emulsions, especially those used on paper supports, are often subject, on processing, and especially on hot glazing, to a form of image discoloration and a reduction of its reflection density. That is, when a blueblack silver image formed by development is subjected to drying by a glazer at high temperature, the silver image is discolored purple or lead-gray and at the same time the reflection density of the silver image is reduced. This phenomenon is usually called plumming.

In order to prevent the formation of the aforesaid discoloration and density reduction, various compounds have been proposed as anti-plumming additives for photographic silver halide light-sensitive emulsions. Examples of anti-plumming agents are 1-phenyl-5-mercaptotetra- Zole, potassium salt of endothiophenylthiadiazolinethiol, and derivatives of 2,3a,5,6a-tetrazaperhydropentalene-1,4- dithione, and so forth.

Generally, the anti-plumming agent is incorporated in a coating composition of a sliver halide light-sensitive emulsion layer or other layers by the following method. The anti-plurnming agentis dissolved into an organic solvent such as methanol, and the resulting solution is added to a silver halide light-sensitive emulsion or an aqueous gelatin solution. Optionally, the anti-plumming agent is added to a silver halide light-sensitive emulsion or an aqueous gelatin solution directly or as an aqueous solution thereof.

However, the addition of some anti-plumming agents is accompanied by a serious reduction in the sensitivity of the photographic silver halide emulsion because of strong adsorption of the anti-plumming agents on the light-sensitive silver halide grains.

Therefore, an object of this invention is to provide a photographic light-sensitive element causing no plumming, that is, causing neither discoloration not density reduction when dried at a high temperature.

Another object of this invention is to provide a photographic silver halide light-sensitive element having a layer containing an anti-plumming agent substantially unaccompanied by the reduction of the sensitivity thereof.

3,585,036 Patented June 15, 1971 Still other objects of this invention will become apparent from the following description.

BRIEF DESCRIPTION OF THE INVENTION According to the present invention there is provided a photographic silver halide light-sensitive element having a layer containing an anti-plumming agent, said antiplumming agent having been incorporated in said layer as a fine dispersion of a solution thereof in a non-volatile organic solvent which is sparingly soluble (less than 0.5 in solubility) in water under the condition of preparation of photographic light-sensitive elements where the pH is below 7 but is dissolved out of the layer under the condition of development where the pH is greater than 8.

That is, the photographic silver halide light-sensitive element of the present invention is prepared by dissolving an anti-plumming agent in the organic solvent having the properties mentioned above (hereinafter such an organic solvent shall be called alkali-philic hydrophobic solvent) directly or by the aid of an auxiliary solvent, dispersing the solution thus prepared into a silver halide emulsion or an aqueous gelatin solution to make a coating composition, and applying it to a support followed by drying. Before development of the photographic light-sensitive element of this invention, the anti-plumming agent is dispersed in an emulsion layer as particles of the solution thereof in an alkali-philic hydrophobic solvent. Hence, the anti-plumming agent is in a protected state in the emulsion layer. The agent is, therefore, prevented from diflfusing into the other layers. Also, since the anti-plumming agent is isolated from the photographic light-sensitive silver halide grains in the photographic light-sensitive element,

the mutual action between anti-plumming agents and silver halide grains is prevented. Hence, storage of the unprocessed photographic light-sensitive element is not accompanied by the deterioration of its photographic properties, for example, by the reduction of its sensitivity. In the course of development (at a pH of higher than 8) the alkali-philic hydrophobic solvent is dissolved out of the layer, and thus the anti-plumming agent now being free from protection by the solvent, exhibits its mutual action with the silver halide grains, i.e., exhibits its anti-plumming action. In other words, according to the present invention, the photographic light-sensitive element containing an anti-plumming agent does not result in deterioration of the photographic properties when it is stored in a non-processed state, and after development, does not show a plumming phenomenon when it is dried by glazing at high temperature.

DETAILED DESCRIPTION OF THE INVENTION vent used in this invention is one represented by the general Formula I NCHCHCOOH RCO X wherein X represents a hydrogen atom or a methyl group and R and R each represents an alkyl group or a substipletely into the alkaline aqueous solution.

Typical examples of the compound shown by general Formula I are shown below:

(1) 2-methyl-3-(N-n-hexylacetamido)-propionic acid;

N--GHzCH-COOH CH; C (3H: (2) 3-[N-(Z-ethylhexyl)acetamido]-propionic acid;

02115 N-CH -CH -CO 0H CHaC O (3) 2-methyl-3-(N-n-octylacetamido)-propionic acid;

n-CaHn NCHZCHGOOH CHaCO CH3 (4) 3-(N-n-butyloctamido)-pr0pionic acid; and

(S) 3-[N (3 hexyloxypropyl)acetamido1-propionic acid;

!1CaHi3OCH CH2CHa N-CHr-CHz-COOH CHsCO These compounds are novel compounds, which may be prepared by the method described below. However, in the present invention, other alkali-philic hydrophobic solvent satisfying the aforesaid requirements may also be employed.

As mentioned above, in the present invention, the aforesaid anti-plumming agent is directly dissolved into the alkali-philic hydrophobic organic solvent or is dissolved therein using an auxiliary solvent. By auxiliary solvent is meant a solvent used for facilitating the dissolution of the anti-plumming agent in the alkali-philic hydrophobic solvent, reducing the viscosity of the solution, and facilitating the preparation of the dispersion. The auxiliary solvent may be water-soluble or volatile and can be removed from the system during the production of the photographic light-sensitive elements, or may be water-insoluble and non-volatile, and hence be left in the lightsensitive element together with the alkali-philic hydrophobic solvent during the production of the light-sensitive elements, provided that it is solublized by the solvent and is dissolved out with the latter during development. If necessary, both types of the auxiliary sol-vent may be employed simultaneously.

As the former type auxiliary solvents, there are mentioned methanol, acetone, dimethylformamide, ethyl acetate, methylethylketone and so on. As examples of the latter type are mentioned phosphoric acid esters or a phthalic acid ester, but a methyl ester or an ethyl ester of the alkali-philic hydrophobic solvent having beforementioned general Formula I (that is, a compound represented by general Formula II RCO X (II) wherein X, R and R have the same meanings as in Formula I and R" represents a methyl group or an ethyl group) is particularly suitable owing to its desirable dissolving power and viscosity.

Typical examples of the auxiliary solvents represented by general Formula II are shown below, which may be obtained as intermediates in the preparation of (I).

4 (6) Ethyl-2-methyl-3-(N n hexylacetamido) propronate;

nCaH

NCHz-CH-C00C2H5 (311306 lfls (7) Ethyl 3-[N-(Z-ethylhexyl)acetamido]-propionate;

CH-CHz CzHs NCH1CHZCOOCZH5 CHsCO (8) Methyl 2-methyl-3-(N n 0ctylacetamido)-propionate;

NCHz-CHCOOCHa CH3C6 (3E3 (9) Methyl S-(N-n-butyloctanamido)-propionate; and

n-CrHn NCHz-OH COO-GH;

I1C1H15CO 10) Methyl 3-[N-(3-hexyloxypropyl)acetamidoJ-propionate;

nCoH 0CHzCHqOH N-CHg-CHr-COO-CHa OHBCO As for the anti-plumming agents, any compound may be used as long as it has a desired anti-plumming effect and requisite solubility in the solvent. Typical examples of the anti-plumming agents usable in this invention are shown below, although the invention is not limited thereto.

(cf.; Japanese patent publication No. 8582/ 1965 for Compounds (ll)( 14) and US. patent specification No. 2,743,184 for Compound (15)).

The preparative procedures of the alkali-philic hydrophobic organic solvent shown as Compounds 1-5 will be shown below.

PREPARATION OF COMPOUND I A mixture of 101 g. of n-hexylamine, 100 g. of methyl methacrylate, and 1 g. of sodium methylate was heated for 2 days to about 70 C. on a water bath and then the resulting solution was subjected to distillation under a reduced pressure to provide 140 g. of methyl 2-hexylaminoisobutyrate as a fraction having a boiling point of 80 C./2 mm. Hg.

To the entire amount of the product was slowly added 84 g. of freshly distilled acetic anhydride. In this case, however, the rate of addition of acetic anhydride was so adjusted that the temperature of the system was maintained lower than 100 C. to avoid excessive heat formation. After the addition of acetic anhydride, the product was heated for another 30 minutes on a water bath and distilled under a reduced pressure to provide 145 g. of a fraction having a boiling point of 130 C./ 1 mm. Hg.

The product thus obtained was mixed with 450 ml. of an aqueous 2 N sodium hydroxide solution containing 45 ml. of methanol and the mixture was shaken at room temperature, whereby the heat was generated and the solution soon became clear. After further shaking of the system, the resulting solution was cooled and acidified with concentrated hydrochloric acid to separate an oily material. This was extracted with ether, washed with water, dried over sodium sulfate, and then the solvent was distilled off under vacuum to provide 120 g. of Compound 1.

Nitrogen analysis.Found: 6.02%. Calculated: 6.11%.

PREPARATION OF COMPOUND 2 While cooling with water, 86 g. of methyl acrylate was added dropwise to 129 g. of 2-ethylhexylamine at 30 C., with stirring. After the end of the addition, the resultant product was heated for one hour on a water bath and then subjected to distillation under a reduced pressure to provide 170 g. of a fraction having a boiling point of 91 C./1 mm. Hg. The fraction was treated with 92 g. of freshly distilled acetic anhydride in the same manner as in the above-mentioned example and then the product was distilled under a reduce pressure to provide 180 g. of a fraction having a boiling point of 140-145 C./1 mm. Hg. The fraction was mixed with 500 ml. of an aqueous 2 N sodium hydroxide solution followed by shaking to cause hydrolysis and to make the solution clear. The resultant product was acidified with hydrochloric acid. The oily product thus formed was extracted with ether, washed with water and dried, and thereafter the solvent was distilled 01f under a reduced pressure to provide 155 g. of Compound 2.

Nitrogen analysis.Found: 5.63%. Calculated: 5.76%.

PREPARATION OF COMPOUND 3 A mixture of 100 g. of n-octylamine, 65 g. of methyl methacrylate, and 1 g. of sodium methylate was heated for 2 days to about 70 C., on a water bath and the resultant product distilled under a reduced pressure to provide 95 g. of an addition product as a fraction of 107 C./l mm. Hg.

The whole amount of the addition product was treated with 58 g. of freshly distilled acetic anhydride as in Example 1 and then distilled under a reduced pressure to provide 94 g. of a fraction having a boiling point of 142 145 C./l mm. Hg. The fraction was hyrolyzed in 250 ml. of an aqueous 2 N sodium hydroxide solution containing 30 ml. of methanol and then treated in the same manner as Example 1 to provide 78 g. of Compound 3.

Nitrogen analysis.Found: 5.29%. Calculated: 5.45%.

PREPARATION OF COMPOUND 4 As in the case of preparing Compound 2, 88 g. of nbutylamine was caused to react with 86 g. of methylacrylate and the product was subjected to a distillation under reduced pressure to provide 123 g. of a fraction having a boiling point of 64 C./5 mm. Hg.

The entire amount of the fraction was dissolved into 2 liters of ether and 100 g. of triethylamine and to this solution, under cooling and stirring, was added 118 g. of octanoyl chloride dropwise. Thereafter, the triethylamine hydrochloride formed was filtered oif and the ether was also removed by distillation. The resultant product was hydrolyzed in 400 ml. of an aqueous 2 N sodium hydroxide solution containing 40 ml. of methanol as in the case of the preparation of Compound 1 and after extracting the product, the ether was removed by distillation and the product was distilled under a reduced pressure to provide 50 g. of Compound 4 as a fraction having a boiling point of 195-203 C./3 mm. Hg.

Nitrogen analysis.Found: 5.23%. Calculated: 5.16%.

PREPARATION OF COMPOUND 5 As in the case of preparation of Compound 2, 53 g. of 3-hexyloxypropylamine (which can be prepared by a method described in the specification of Japanese Pat. No. 27,563/ 1964) was treated with 28 g. of methyl acrylate and the resulting product was distilled under a reduced pressure to provide 71 g. of an addition product as a fraction having a boiling point of 96 C./1 mm. Hg. The whole amount of the addition product was mixed with 35 g. of freshly distilled acetic anhydride followed by heating for 30 minutes to 70 C. The product was subjected to distillation under a reduced pressure to provide 73 g. of the acetylated product having a boiling point of 149 C./1 mm. Hg. The acetylated product was hydrolyzed in 150 ml. of an aqueous 2 N sodium hydroxide solution containing 15 m1. of methanol. The product was extracted with ether, washed with water, dried, and the solvent was distilled ofl? under vacuum to provide 61 g. of Compound 5.

Nitrogen analysis.Found: 4.99%. Calculated: 5.13%.

The invention will be illustrated by the following nonlimiting practical examples.

EXAMPLE 1 After addition of suitable amounts of an antifoggant, a stabilizer and a hardening agent, a photographic silver halide emulsion containing 4.0 g. of a silver halide (silver chloro-bromide consisting of 50 mol percent of silver chloride and 50 mol percent of silver bromide) and 11.0 g. of gelatin per 100 g. of the emulsion was applied to a photographic baryta paper and dried. (Emulsion I).

On the other hand, a photographic emulsion was mixed with 10 ml. (per 100 g. of said emulsion) of a 0.3% methanol solution of Compound 11. 3,6-diphenyl-2,3a,5, 6a-tetrazaperhydropentalene 1,4 dithione and suitable amount of additives and was applied to a photographic baryta paper and dried (Emulsion II).

Further, 0.03 g. of aforesaid Compound 11 was dissolved into 1 ml. of methanol and the solution thus obtained was mixed uniformly with 2.5 g. of the alkali-philic hydrophobic solvent shown as Compound 2, 3-[N-(2- ethylhexyl)acetamido1propionic acid. The solution was added to 100 g. of aforesaid photographic emulsion 1 and, after adding suitable amounts of additives, the resulting emulsion was applied to photographic baryta paper. (Emulsion III).

Each of the three kinds of the photographic lightsensitive papers prepared above was exposed, developed for seconds at 20 C., in a usual developer for photographic paper, fixed, subjected to glazing at C., and then the sensitivity and the maximum reflection density thereof were measured. The sensitivity was based on the reciprocal multiplied by 100 of the exposure (C.M.S.) necessary for obtaining the density of 1.0. The results are shown in the following table:

The results showed that Emulsion H showed a high anti-plumming effect as compared with Emulsion I, but the sensitivity thereof was reduced to about 40% of that of Emulsion I. On the other hand, in Emulsion III of this invention, the plumming effect sufficiently prevented and also the reduction in sensitivity was only about that of Emulsion I.

EXAMPLE 2 After adding suitable amounts of an antifoggant, a stabilizer and a hardening agent, a photographic emulsion containing 4.5 g. of a silver halide per 100 g. of emulsion was applied to a photographic baryta paper and dried. (Emulsion IV).

30 ml. of the potassium salt of 5-mercapto-3-phenyl-2- thiol-1,3,4-thiazolone shown as Compound was dissolved into 2 ml. of methanol and the resulting solution was added to 100 g. of Emulsion IV. After further adding suitable amounts of additives, the photographic lightsensitive emulsion thus prepared was applied to a photographic baryta paper and dried. (Emulsion V).

Further, 30 mg. of the anti-plumming agent. Compound 15, was dissolved into 2 ml. of methanol and the solution thus formed was uniformly mixed with 2.5 g. of the alkali-philic hydrophobic solvent shown as Compound 5, 3 [N (3 hexyloxypropyl)acetamido]propionic acid by using the 0.5 g. of Compound 6, ethyl 2- methyl-3-(N-n-hexylacetamido)-propionate as the auxiliary solvent. The resulting composition was added to 100 g. of photographic Emulsion IV prepared above and after addition of suitable amounts of additives, the photographic light-sensitive emulsion was applied to a photographic baryta paper and dried. (Emulsion VI).

The three kinds of the photographic light-sensitive papers prepared above were processed as in Example 1 and the results are shown in the following table:

Maximum Thus, in Emulsion V, the plumming effect was prevented as compared with the case of using Emulsion 'IV, but the sensitivity was reduced to about 40% of Emulsion IV. On the other hand, in Emulsion VI of the present invention, the plumming was sufficiently prevented and the sensitivity thereof was reduced to only about 15% of Emulsion IV.

What is claimed is:

1. A photographic silver halide light-sensitive element comprising a support having a silver halide emulsion layer and said support bearing at least one layer containing at least one anti-plumming agent and a non-volatile organic solvent having the formula:

wherein at is hydrogen or methyl and R and R are each alkyl groups or R is an alkoxyalkyl group, the total carbon atoms contained in R and R being 7 to 11, said solvent being substantially sparingly soluble in water at a pH lower than 7, but which is dissolved out of said at least one layer at a pH higher than 8, said at least one layer being applied from a coating composition wherein said agent is present in said composition as a fine dispersion of a solution thereof in the said solvent.

2. The photographic silver halide light-sensitive element according to claim 1, wherein said solvent is selected from the group consisting of:

2-methyl-3-(N-n-hexylacetamido)-propionic acid, 3- [N- (2-ethylhexyl) acetamido] -propionic acid, 2-methyl-3- (N-n-octylacetamido -propionic acid, 3-(N-n-butyloctanamido)propionic acid, and

3- [N-( 3-hexyloxypropyl) acetamido] -propionic acid.

3. The photographic silver halide light-sensitive element according to claim 1, wherein said solution of antiplumming agent in an organic solvent is prepared by adding the anti-plumming agent directly to said nonvolatile organic solvent.

4. The photographic silver halide light-sensitive element according to claim 1, wherein said solution of antiplumming agent in an organic solvent is prepared by adding the anti-plumming agent to said non volatile organic solvent as a solution in an auxiliary solvent.

5. The photographic silver halide light-sensitive element according to claim 4, wherein said auxiliary solvent is selected from the group consisting of methanol, acetone, dimethylforrnamide, ethyl acetate, methylethylketone, and a compound of the following general Formula II:

RCO X wherein X represents a hydrogen atom or a methyl group, R and R each represents an alkyl group or R is an alkoxyalkyl group, the total carbon number of R and R being from 7 to 11, and R" represents a methyl group or an ethyl group.

6. The photographic silver halide light-sensitive element according to claim 5, wherein said compound represented the general Formula II is selected from the group consisting of ethyl 2-methyl-3-(N-n-hexylacetamido)propionate, ethyl 3- [N- (Z-ethylhexyl) acetamido] -propionate, methyl 2-methyl-3-(N-n-octylacetamido)-propionate, methyl 3-(n-n-butyloctanamido)-propionate, and methyl 3-[N-(3-hexyloxypropyl) acetamido] -propionate.

References Cited UNITED STATES PATENTS 2,240,471 4/1941 Swan 96-1145 2,684,954 7/1954 Miller 260-534 2,697,040 12/1954 Parnell 96-52 3,133,816 5/1964 Ben Ezra 96-1145 3,038,804 6/1962 Knox et a1. 96-111X 3,306,749 2/1967 Knox et al. 96-1145 NORMAN G. TORCHIN, Primary Examiner C. L. BOWERS, JR., Assistant Examiner U.S. Cl. X.R. 

